WO2024115134A1 - Process and composition for chemical recycling of polymers having reduced nitrogen and oxygen content - Google Patents
Process and composition for chemical recycling of polymers having reduced nitrogen and oxygen content Download PDFInfo
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- WO2024115134A1 WO2024115134A1 PCT/EP2023/082175 EP2023082175W WO2024115134A1 WO 2024115134 A1 WO2024115134 A1 WO 2024115134A1 EP 2023082175 W EP2023082175 W EP 2023082175W WO 2024115134 A1 WO2024115134 A1 WO 2024115134A1
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- tetramethyl
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Definitions
- the present invention relates to a process for chemical recycling of polymers.
- the invention further relates to a composition of polymers that is suitable for use in chemical recycling processes, in particular in chemical recycling processes involving pyrolysis of polymer compositions to obtain pyrolysis oils and subsequent processing of such pyrolysis oils via steam cracking or via refinery operations to obtain chemical feed streams for the production of polymers.
- streams of polymer materials that one can access contain a wide variety of polymers of different chemical constitution, due to the fact that such streams are typically collected in a combined way; at the user level, e.g. the household, the knowledge and means that would allow the user to separate one type of polymer from the other generally is not available, nor can likely be expected to be available.
- compositions of waste polymers of varying chemical nature can be processed via routes of desirably high value and desirably low environmental impact.
- a particular route via which mixed streams of waste polymers can be processed that is gaining traction is via chemical recycling routes.
- Such routes typically involve a first stage of processing waste polymer streams of certain, defined, composition to produce one or more chemical compositions of oily nature, for example compositions that would be comparable to naphtha-type compositions as one can obtain from refining fossil crude oils, which stage then may be followed by the processing of such oily compositions via thermochemical decomposition processes to obtain hydrocarbon chemical compositions comprising a slate of chemicals that can be used again for manufacturing new, or ‘virgin’, products, including ‘virgin’ polymer materials such as for example polyethylenes and polypropylenes.
- Such chemical recycling routes can be considered as a (part of) a solution for dealing with the abundantly available waste plastics streams.
- the composition of the waste plastics streams can affect the efficiency of the operation of such chemical recycling routes.
- a particular element that may be detrimental to the capability of processing waste plastics via chemical recycling routes is nitrogen.
- the presence of nitrogen may lead to disruptions in the operation of equipment that is employed in unit operations for production of chemical compositions comprising ethylene and propylene, such as in steam cracking operations.
- processes of the art provide for separate unit operations to capture nitrogen-containing compounds at various stages of the chemical recycling process.
- stages may include hydrotreatment stages, and polishing stages.
- hydrotreatment stages and polishing stages.
- polishing stages As will be understood, in view of process efficiency it is preferred to minimise additional stages that need to be used in such chemical recycling process; each stage comes at a cost, involves additional consumption of energy, and leads to reduction of the yield of the process. Therefore, it is desired to employ a process in which the least amount of unit operations or process stages have to be incorporated.
- the inventors of the present application have now found a particularly suitable process for chemical recycling, wherein the process involves the steps of: i. supplying a composition of polymers; ii. subjecting the composition of polymers to a thermal treatment to obtain a pyrolysis oil; iii. optionally, subjecting the product obtained in step ii. to a hydrotreatment process; iv. subjecting the product obtained in step ii., or, when applied, the product obtained in step iii.
- stabilisation compound(s) comprising both oxygen atoms and nitrogen atoms are present only to such amount that such stabilisation compound(s) attribute to at most 20 ppm of nitrogen atoms and at most 50 ppm of oxygen atoms, with regard to the total weight of the composition of polymers.
- Such process allows for efficient chemical recycling of polymers, using a simplified process, wherein the fouling of the equipment employed in the process is reduced.
- the chemical recycling involves steam cracking
- such process allows for the use of an increased fraction of the product of step ii., e.g. a pyrolysis oil product, and/or the product of step iii, e.g. a hydrotreated pyrolysis oil product, without detrimental effects on the steam cracking process, such as reduction of service life of the steam cracker, or fouling.
- the stabilisation compound(s) attribute to at most 15 ppm of nitrogen atoms, more preferably at most 10 ppm, even more preferably at most 5 ppm, in the composition of polymers, with regard to the total weight of the composition of polymers.
- the stabilisation compound(s) attribute to > 5 ppb and ⁇ 15 ppm of nitrogen atoms, more preferably > 5 ppb and ⁇ 10 ppm, even more preferably > 5 ppb and ⁇ 5 ppm, in the composition of polymers, with regard to the total weight of the composition of polymers.
- the stabilisation compound(s) attribute to > 5 ppb and ⁇ 40 ppm of oxygen atoms, more preferably > 5 ppb and ⁇ 30 ppm, even more preferably > 5 ppb and ⁇ 20 ppm, in the composition of polymers, with regard to the total weight of the composition of polymers.
- the stabilisation compound(s) may attribute to
- the stabilisation compound(s) are compounds comprising one or more moiety(ies) according to formula I:
- the stabilisation compound(s) may be selected from bis(2, 2,6,6- tetramethyl-4-piperidinyl) sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1 , 2,2,6, 6-pentamethyl-4- piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butyl malonate, 1 ,2,2,6, 6-pentamethyl- 4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, 2,2,6,6-tetramethyl-4- piperidyl methacrylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1 ,2,3,4- butanetetracarboxylate, bis(1-
- the composition of polymer may comprise ⁇ 5000 ppm by weight of the stabilisation compound(s), preferably > 500 and ⁇ 5000 ppm, more preferably > 500 and ⁇ 3000 ppm, with regard to the total weight of the composition of polymers.
- the composition of polymers comprises an amount of stabilisation compound(s) comprising both oxygen atoms and nitrogen atoms so that the composition of polymers comprises > 1 ppb by weight or oxygen atoms and > 1 ppb by weight of nitrogen atoms attributable to the stabilisation compound(s), preferably > 5 ppb by weight or oxygen atoms and > 5 ppb by weight of nitrogen atoms, with regard to the total weight of the composition of polymers.
- the thermal treatment of step ii. may for example involve a low-severity pyrolysis process, wherein the pyrolysis of the composition of polymers is performed at a temperature of > 250°C and ⁇ 450°C, or a high-severity pyrolysis process, wherein the pyrolysis of the composition of polymers is performed at a temperature of > 450°C and ⁇ 650°C.
- the thermal treatment may be a catalytic process, preferably wherein the thermal treatment is a process operated in the presence of a ZSM-5 zeolite catalyst and/or a spent FCC catalyst.
- the hydrotreatment step iii. may be performed at a temperature of ⁇ 350°C, in the presence of hydrogen, preferably at a pressure of ⁇ 10.0 MPa, preferably > 1 .0 and ⁇ 10.0 MPa, more preferable at > 2.0 and ⁇ 7.0 MPa.
- the hydrotreatment step iii. may be performed in the presence of a catalyst, wherein the catalyst is selected from a cobalt-molybdenum catalyst on alumina support, a nickel-molybdenum catalyst on alumina support, a tungsten-molybdenum catalyst on alumina support, a platinum-palladium catalyst on alumina support, a nickel sulphide catalyst, a molybdenum sulphide catalyst, or a nickel-molybdenum sulphide catalyst.
- the catalyst is selected from a cobalt-molybdenum catalyst on alumina support, a nickel-molybdenum catalyst on alumina support, a tungsten-molybdenum catalyst on alumina support, a platinum-palladium catalyst on alumina support, a nickel sulphide catalyst, a molybdenum sulphide catalyst, or a nickel-molybdenum sulphide catalyst.
- the thermal decomposition process of step iv. may be a steam cracking process, preferably wherein the steam cracking occurs in a steam cracking unit comprising heated coils, wherein the coil outlet temperature (COT) is in the range of 800°C to 870°C.
- the thermal decomposition process of step iv. may be a catalytic cracking process.
- the feed composition that is supplied to the steam cracking process may for example comprise > 2.5 wt% and ⁇ 75.0 wt%, preferably > 5.0 wt% and ⁇ 50.0 wt%, more preferably > 10.0 wt% and ⁇ 50.0 wt% of the product obtained in step ii.
- the feed composition that is supplied to the steam cracking process may for example comprise > 2.5 wt% and ⁇ 75.0 wt%, preferably > 5.0 wt% and ⁇ 50.0 wt%, more preferably > 10.0 wt% and ⁇ 50.0 wt% of the product obtained in step iii.
- composition of polymers may for example comprise:
- composition of polymers • at most 20 ppm of nitrogen atoms, preferably > 1 ppb and ⁇ 20 ppm; and • at most 50 ppm of oxygen atoms, preferably > 1 ppb and ⁇ 50 ppm with regard to the total weight of the composition of polymers; preferably wherein the composition is obtained as a waste plastics stream from postconsumer wastes.
- the invention also relates to a composition of polymers comprising:
- stabilisation compound(s) comprising both oxygen atoms and nitrogen atoms to such amount that such stabilisation compound(s) attribute to at most 20 ppm of nitrogen atoms and at most 50 ppm of oxygen atoms; with regard to the total weight of the composition of polymers; preferably wherein the composition is obtained as a waste plastics stream from postconsumer wastes.
- composition of polymers may for example comprise one or more stabilisation compound(s), wherein the stabilisation compound(s) are compounds comprising one or more moiety(ies) according to formula I:
- the stabilisation compound(s) may for example be selected from bis(2, 2,6,6- tetramethyl-4-piperidinyl) sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1 , 2,2,6, 6-pentamethyl-4- piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butyl malonate, 1 ,2,2,6, 6-pentamethyl- 4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, 2,2,6,6-tetramethyl-4- piperidyl methacrylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1 , 2,3,4- butanetetracarboxylate, bis(1-oxy
- composition of polymers is obtained as a waste plastics stream, for example from post-consumer or household wastes.
- the invention also relates to the use of a composition of polymers according to the invention for the reduction of fouling and/or corrosion during steam cracking of chemical feeds comprising waste plastics-derived materials.
- Such process allows for efficient chemical recycling of polymers, using a simplified process, wherein the corrosion of the equipment employed in the process is reduced.
- the hydrotreatment process of step iii. may for example be performed in one of more vessel(s) configured to hold a hydrotreatment catalyst.
- the vessel may be configured to operate in gas phase, liquid phase, vapour-liquid phase, or slurry phase.
- the vessel may include one or more beds of the hydrotreatment catalyst.
- Such bed(s) may be fixed bed(s), fluidized bed(s), moving bed(s), slurry bed(s), or combinations thereof.
- the vessel may be operated in adiabatic, isothermal, non-adiabatic, or nonisothermal conditions.
- the product of step ii. may be subjected to treatment in the presence of hydrogen, wherein the volume flow ratio of hydrogen to the product of step ii. may for example be 10 to 3000, preferably 200 to 1000.
- the hydrotreatment step iii may be performed in the presence of a catalyst.
- Such catalyst may for example be a catalyst selected from a cobalt-molybdenum catalyst on alumina support, a nickel-molybdenum catalyst on alumina support, a tungstenmolybdenum catalyst on alumina support, a platinum-palladium catalyst on alumina support, a nickel sulphide catalyst, a molybdenum sulphide catalyst, or a nickelmolybdenum sulphide catalyst.
- the catalyst that may be used in the hydrotreatment step iii. may for example be sulphided.
- the composition of polymers preferably comprises > 70.0 wt% of polyolefins.
- polyolefins preferably comprise polyethylenes and polypropylenes.
- the polyolefins may comprise > 80.0 wt% of polyethylenes, or > 90.0 wt% of polyethylenes.
- the polyolefins may comprise ⁇ 20.0 wt% of polypropylenes, or ⁇ 10.0 wt% of polypropylenes.
- Such polyethylenes may be a composition comprising low-density polyethylenes, linear low-density polyethylenes, and high-density polyethylenes.
- the composition of polymers comprises a high fraction of polyolefins, such as > 70.0 wt%, or > 80.0 wt%, or > 90.0 wt%, with regard to the total weight of the composition of polymers.
- Compositions of polymers comprising such high fraction of polyolefins are particularly suitable for chemical recycling via catalytic or non-catalytic thermal treatment processes, due to the fact that their polymer structure is based on linear monomers, which are suitable for thermal cracking.
- the composition of plastics in particular a composition of waste plastics, may be converted into chemical building blocks, in particular ethylene and propylene.
- the process of the present invention allows for the suitable conversion of waste plastics into new plastics of high quality, thereby creating a circular economy of material use.
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
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Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP23808784.5A EP4627004A1 (en) | 2022-11-28 | 2023-11-17 | Process and composition for chemical recycling of polymers having reduced nitrogen and oxygen content |
| CN202380081943.9A CN120344636A (en) | 2022-11-28 | 2023-11-17 | Methods and compositions for chemical recovery of polymers having reduced nitrogen and oxygen contents |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP22209975 | 2022-11-28 | ||
| EP22209975.6 | 2022-11-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024115134A1 true WO2024115134A1 (en) | 2024-06-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2023/082175 Ceased WO2024115134A1 (en) | 2022-11-28 | 2023-11-17 | Process and composition for chemical recycling of polymers having reduced nitrogen and oxygen content |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP4627004A1 (en) |
| CN (1) | CN120344636A (en) |
| WO (1) | WO2024115134A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190002664A1 (en) * | 2015-12-18 | 2019-01-03 | Solvay Sa | Process for producing waxes and liquid fuels from waste plastic |
| WO2021105326A1 (en) * | 2019-11-29 | 2021-06-03 | Neste Oyj | Two-step process for converting liquefied waste plastics into steam cracker feed |
| WO2022017903A1 (en) * | 2020-07-20 | 2022-01-27 | Sabic Global Technologies B.V. | Process for the preparation of butenes and butadienes from waste plastic feedstocks. |
-
2023
- 2023-11-17 CN CN202380081943.9A patent/CN120344636A/en active Pending
- 2023-11-17 EP EP23808784.5A patent/EP4627004A1/en active Pending
- 2023-11-17 WO PCT/EP2023/082175 patent/WO2024115134A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190002664A1 (en) * | 2015-12-18 | 2019-01-03 | Solvay Sa | Process for producing waxes and liquid fuels from waste plastic |
| WO2021105326A1 (en) * | 2019-11-29 | 2021-06-03 | Neste Oyj | Two-step process for converting liquefied waste plastics into steam cracker feed |
| WO2022017903A1 (en) * | 2020-07-20 | 2022-01-27 | Sabic Global Technologies B.V. | Process for the preparation of butenes and butadienes from waste plastic feedstocks. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN120344636A (en) | 2025-07-18 |
| EP4627004A1 (en) | 2025-10-08 |
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